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Julia Burdge
Michelle Driessen

Introductory
Chemistry
AN ATOMS FIRST APPROACH

Second Edition
Fundamental Constants
Avogadro’s number (NA) 6.0221418 × 1023
Electron charge (e) 1.6022 × 10−19 C
Electron mass 9.109387 × 10−28 g
Faraday constant (F) 96,485.3 C/mol e−
Gas constant (R) 0.0821 L ⋅ atm/K ⋅ mol
8.314 J/K ⋅ mol
62.36 L ⋅ torr/K ⋅ mol
1.987 cal/K ⋅ mol
Planck’s constant (h) 6.6256 × 10−34 J ⋅ s
Proton mass 1.672623 × 10−24 g
Neutron mass 1.674928 × 10−24 g
Speed of light in a vacuum 2.99792458 × 108 m/s

Some Prefixes Used with SI Units

tera (T) 1012 centi (c) 10−2
giga (G) 109 milli (m) 10−3
mega (M) 106 micro ( µ) 10−6
kilo (k) 103 nano (n) 10−9
deci (d) 10−1 pico (p) 10−12

Useful Conversion Factors and Relationships

1 lb = 453.6 g
1 in = 2.54 cm (exactly)
1 mi = 1.609 km
1 km = 0.6215 mi
1 pm = 1 × 10−12 m = 1 × 10−10 cm
1 atm = 760 mmHg = 760 torr = 101,325 N/m2 = 101,325 Pa
1 cal = 4.184 J (exactly)
1 L ⋅ atm = 101.325 J
1J=1C×1V
5°C
?°C = (°F − 32°F) ×
9°F
9°F
?°F = × (°C) + 32°F
5°C

?K = (°C + 273.15°C) (
1°C )
1K
 Periodic Table of the Elements
Main group Main group

Period 1A Group
number number 8A
1
18
1 Key 2
1 H
Hydrogen 6 3A 4A 5A 6A 7A
He 1
2A Atomic number Symbol Helium
1.008 2 13 14 15 16 17
C 4.003
3 4 Carbon 5 6 7 8 9 10
Name 12.01 Average
2 Li Be atomic mass B C N O F Ne 2
Lithium Beryllium An element Boron Carbon Nitrogen Oxygen Fluorine Neon
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 Transition metals 13 14 15 16 17 18
3 Na Mg 3B 4B 5B 6B 7B 8B 1B 2B
Al Si P S Cl Ar 3
Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine Argon
22.99 24.31 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 4
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.41 69.72 72.64 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 5
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 6
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
132.9 137.3 138.9 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og 7
Francium Radium Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
(223) (226) (227) (267) (268) (271) (272) (270) (276) (281) (280) (285) (286) (289) (289) (293) (293) (294)

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Metals Lanthanides 6 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 6
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
140.1 140.9 144.2 (145) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
Nonmetals
90 91 92 93 94 95 96 97 98 99 100 101 102 103

Metalloids Actinides 7 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 7
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
232.0 231.0 238.0 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)
 List of the Elements with Their Symbols and Atomic Masses*
Element Symbol Atomic Number Atomic Mass† Element Symbol Atomic Number Atomic Mass†
Actinium Ac 89 (227) Mendelevium Md 101 (258)
Aluminum Al 13 26.9815386 Mercury Hg 80 200.59
Americium Am 95 (243) Molybdenum Mo 42 95.94
Antimony Sb 51 121.760 Moscovium Mc 115 (289)
Argon Ar 18 39.948 Neodymium Nd 60 144.242
Arsenic As 33 74.92160 Neon Ne 10 20.1797
Astatine At 85 (210) Neptunium Np 93 (237)
Barium Ba 56 137.327 Nickel Ni 28 58.6934
Berkelium Bk 97 (247) Nihonium Nh 113 (286)
Beryllium Be 4 9.012182 Niobium Nb 41 92.90638
Bismuth Bi 83 208.98040 Nitrogen N 7 14.0067
Bohrium Bh 107 (272) Nobelium No 102 (259)
Boron B 5 10.811 Oganesson Og 118 (294)
Bromine Br 35 79.904 Osmium Os 76 190.23
Cadmium Cd 48 112.411 Oxygen O 8 15.9994
Calcium Ca 20 40.078 Palladium Pd 46 106.42
Californium Cf 98 (251) Phosphorus P 15 30.973762
Carbon C 6 12.0107 Platinum Pt 78 195.084
Cerium Ce 58 140.116 Plutonium Pu 94 (244)
Cesium Cs 55 132.9054519 Polonium Po 84 (209)
Chlorine Cl 17 35.453 Potassium K 19 39.0983
Chromium Cr 24 51.9961 Praseodymium Pr 59 140.90765
Cobalt Co 27 58.933195 Promethium Pm 61 (145)
Copernicium Cn 112 (285) Protactinium Pa 91 231.03588
Copper Cu 29 63.546 Radium Ra 88 (226)
Curium Cm 96 (247) Radon Rn 86 (222)
Darmstadtium Ds 110 (281) Rhenium Re 75 186.207
Dubnium Db 105 (268) Rhodium Rh 45 102.90550
Dysprosium Dy 66 162.500 Roentgenium Rg 111 (280)
Einsteinium Es 99 (252) Rubidium Rb 37 85.4678
Erbium Er 68 167.259 Ruthenium Ru 44 101.07
Europium Eu 63 151.964 Rutherfordium Rf 104 (267)
Fermium Fm 100 (257) Samarium Sm 62 150.36
Flerovium Fl 114 (289) Scandium Sc 21 44.955912
Fluorine F 9 18.9984032 Seaborgium Sg 106 (271)
Francium Fr 87 (223) Selenium Se 34 78.96
Gadolinium Gd 64 157.25 Silicon Si 14 28.0855
Gallium Ga 31 69.723 Silver Ag 47 107.8682
Germanium Ge 32 72.64 Sodium Na 11 22.98976928
Gold Au 79 196.966569 Strontium Sr 38 87.62
Hafnium Hf 72 178.49 Sulfur S 16 32.065
Hassium Hs 108 (270) Tantalum Ta 73 180.94788
Helium He 2 4.002602 Technetium Tc 43 (98)
Holmium Ho 67 164.93032 Tellurium Te 52 127.60
Hydrogen H 1 1.00794 Tennessine Ts 117 (293)
Indium In 49 114.818 Terbium Tb 65 158.92535
Iodine I 53 126.90447 Thallium Tl 81 204.3833
Iridium Ir 77 192.217 Thorium Th 90 232.03806
Iron Fe 26 55.845 Thulium Tm 69 168.93421
Krypton Kr 36 83.798 Tin Sn 50 118.710
Lanthanum La 57 138.90547 Titanium Ti 22 47.867
Lawrencium Lr 103 (262) Tungsten W 74 183.84
Lead Pb 82 207.2 Uranium U 92 238.02891
Lithium Li 3 6.941 Vanadium V 23 50.9415
Livermorium Lv 116 (293) Xenon Xe 54 131.293
Lutetium Lu 71 174.967 Ytterbium Yb 70 173.04
Magnesium Mg 12 24.3050 Yttrium Y 39 88.90585
Manganese Mn 25 54.938045 Zinc Zn 30 65.409
Meitnerium Mt 109 (276) Zirconium Zr 40 91.224
*These atomic masses show as many significant figures as are known for each element. The atomic masses in the periodic table are shown to four significant figures, which is
sufficient for solving the problems in this book.
†Approximate values of atomic masses for radioactive elements are given in parentheses.
 Introductory
Chemistry
An Atoms First Approach
SECOND EDITION

Julia Burdge
COLLEGE OF WESTERN IDAHO

Michelle Driessen
UNIVERSITY OF MINNESOTA
INTRODUCTORY CHEMISTRY
Published by McGraw-Hill Education, 2 Penn Plaza, New York, NY 10121. Copyright © 2020 by McGraw-Hill
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To the people who will always matter the most: Katie, Beau, and Sam.
—Julia Burdge

To my family, the center of my universe and happiness, with special thanks to my husband for his
support and making me the person I am today.
—Michelle Driessen

And in memory of Raymond Chang. He was a brilliant educator, a prolific writer, an extraordinary
mentor, and a dear friend.
—Julia Burdge and Michelle Driessen
About the Authors

Julia Burdge holds a Ph.D. (1994) from The University of Idaho in

Moscow, Idaho; and a Master’s Degree from The University of South Florida.
Her research interests have included synthesis and characterization of cisplatin
analogues, and development of new analytical techniques and instrumentation
for measuring ultra-trace levels of atmospheric sulfur compounds.
©David Spurgeon
She currently holds an adjunct faculty position at The College of Western
Idaho in Nampa, Idaho, where she teaches general chemistry using an atoms
first approach; but spent the lion’s share of her academic career at The
University of Akron in Akron, Ohio, as director of the Introductory Chemistry
program. In addition to directing the general chemistry program and supervising
the teaching activities of graduate students, Julia established a future-faculty
development program and served as a mentor for graduate students and
postdoctoral associates.

Julia relocated back to the Northwest to be near family. In her free time, she
enjoys precious time with her three children, and with Erik Nelson, her husband
and best friend.

Michelle Driessen earned a Ph.D. in 1997 from the

University of Iowa in Iowa City, Iowa. Her research and dissertation focused on
the thermal and photochemical reactions of small molecules at the surfaces
of metal nanoparticles and high surface area oxides.

Following graduation, she held a tenure-track teaching and research position

at Southwest Missouri State University for several years. A family move took
Courtesy of Michelle Driessen
her back to her home state of Minnesota where she held positions as adjunct
faculty at both St. Cloud State University and the University of Minnesota. It
was during these adjunct appointments that she became very interested in
chemical education. Over the past several years she has transitioned the
general chemistry laboratories at the University of Minnesota from verification
to problem-based, and has developed both online and hybrid sections of
general chemistry lecture courses. She is currently the Director of General
Chemistry at the University of Minnesota where she runs the general chemistry
laboratories, trains and supervises teaching assistants, and continues to
experiment with active learning methods in her classroom.

Michelle and her husband love the outdoors and their rural roots. They take
every opportunity to visit their family, farm, and horses in rural Minnesota.

viii
 Brief Contents
1 Atoms and Elements 2
2 Electrons and the Periodic Table 30
3 Compounds and Chemical Bonds 74
4 How Chemists Use Numbers 122
5 The Mole and Chemical Formulas 164
6 Molecular Shape 196
7 Solids, Liquids, and Phase Changes 238
8 Gases 272
9 Physical Properties of Solutions 312
10 Chemical Reactions and Chemical Equations 348
11 Using Balanced Chemical Equations 386
12 Acids and Bases 420
13 Equilibrium 458
14 Organic Chemistry 484
15 Biochemistry 510
16 Nuclear Chemistry 526
17 Electrochemistry 542

Appendix Mathematical Operations A-1

Glossary G-1
Answers to Odd-Numbered Problems AP-1
Index I-1
Contents
Preface xx

1 ATOMS AND ELEMENTS 2

1.1 The Study of Chemistry 3
• Why Learn Chemistry? 3
• The Scientific Method 3
1.2 Atoms First 5
1.3 Subatomic Particles and the
Nuclear Model of the Atom 6
1.4 Elements and the Periodic Table 10
■ Elements in the Human Body 11
■ Helium 13
1.5 Organization of the Periodic Table 14
■ Elements in Earth’s Crust 15
1.6 Isotopes 16
■ Mass Spectrometry 17
1.7 Atomic Mass 19 ©rozbyshaka/Getty Images

■ Iron-Fortified Cereal 20

2 ELECTRONS AND THE PERIODIC TABLE 30

2.1 The Nature of Light 31
■ Laser Pointers 33
2.2 The Bohr Atom 34
Visualizing Chemistry – Bohr Atom 36
■ Fireworks 38
■ The Photoelectric Effect 39
2.3 Atomic Orbitals 40
• s orbitals 43 • p orbitals 43
• d and f orbitals 44
2.4 Electron Configurations 46
2.5 Electron Configurations and the ©McGraw-Hill Education/David A. Tietz

Periodic Table 51
2.6 Periodic Trends 55
2.7 Ions: The Loss and Gain of Electrons 61
• Electron Configuration of Ions 61
• Lewis Dot Symbols of Ions 63

x
3 COMPOUNDS AND CHEMICAL BONDS 74
3.1 Matter: Classification and Properties 75
• States of Matter 75 • Mixtures 76
• Properties of Matter 78
3.2 Ionic Bonding and Binary Ionic
Compounds 81
3.3 Naming Ions and Binary Ionic
Compounds 85
• Naming Atomic Cations 86
• Naming Atomic Anions 87
• Naming Binary Ionic Compounds 87
3.4 Covalent Bonding and Molecules 89
• Covalent Bonding 90 • Molecules 90
• Molecular Formulas 93
■ Fixed Nitrogen in Fertilizers 96 ©Shutterstock/EpicStockMedia

3.5 Naming Binary Molecular Compounds 97

3.6 Covalent Bonding in Ionic Species: Polyatomic Ions 99
■ Product Labels 100
■ Product Labels 101
■ Hydrates 104
3.7 Acids 105
3.8 Substances in Review 107

Visualizing Chemistry – Properties of Atoms 108

• Distinguishing Elements and Compounds 110

• Determining Whether a Compound Is Ionic or Molecular 111
• Naming Compounds 111
4 HOW CHEMISTS USE NUMBERS 122
4.1 Units of Measurement 123
• Base Units 123 • Mass, Length, and Time 124
• Metric Multipliers 124
■ Henrietta Swan Leavitt 125
• Temperature 128
■ The Fahrenheit Temperature Scale 129
4.2 Scientific Notation 132
• Very Large Numbers 133 • Very Small
Numbers 134 • Using the Scientific Notation
Function on Your Calculator 135
4.3 Significant Figures 137
• Exact Numbers 137 • Measured Numbers 137
■ Arthur Rosenfeld 141
• Calculations with Measured Numbers 142
©David Clapp/Oxford Scientific/Getty Images
4.4 Unit Conversion 146
• Conversion Factors 146
■ The Importance of Units 148
• Derived Units 149
■ The International Unit 151
• Dimensional Analysis 152
4.5 Success in Introductory Chemistry Class 154

5 THE MOLE AND CHEMICAL FORMULAS 164

5.1 Counting Atoms by Weighing 165
• The Mole (The “Chemist’s Dozen”) 165
• Molar Mass 167 • Interconverting Mass,
Moles, and Numbers of Atoms 169
5.2 Counting Molecules by Weighing 171
• Calculating the Molar Mass of a
Compound 171 • Interconverting Mass, Moles,
and Numbers of Molecules (or Formula
Units) 173 • Combining Multiple Conversions
in a Single Calculation 175
■ Redefining the Kilogram 177
■ Derek Muller 178
5.3 Mass Percent Composition 178
©epa european pressphoto agency b.v./Alamy
■ Iodized Salt 180
5.4 Using Mass Percent Composition to Determine Empirical
Formula 181
■ Fertilizer & Mass Percents 183
5.5 Using Empirical Formula and Molar Mass to Determine
Molecular Formula 184
xii
6 MOLECULAR SHAPE 196
6.1 Drawing Simple Lewis Structures 197
• Lewis Structures of Simple Molecules 197
• Lewis Structures of Molecules with a Central
Atom 199 • Lewis Structures of Simple
Polyatomic Ions 199
6.2 Lewis Structures Continued 202
• Lewis Structures with Less Obvious Skeletal
Structures 202 • Lewis Structures with Multiple
Bonds 203 • Exceptions to the Octet Rule 204
■ Bleaching, Disinfecting, and
Decontamination 204
6.3 Resonance Structures 205
6.4 Molecular Shape 207
©Robin Treadwell/Science Source
■ Flavor, Molecular Shape, and Bond-Line
Structures 208
• Bond Angles 212
■ Molecular Shapes Resulting from Expanded Octets 213
6.5 Electronegativity and Polarity 215
• Electronegativity 215 • Bond Polarity 217
• Molecular Polarity 219
■ How Bond Dipoles Sum to Determine Molecular Polarity 221
6.6 Intermolecular Forces 222
• Dipole-Dipole Forces 222 • Hydrogen Bonding 223
• Dispersion Forces 225
■ Linus Pauling 227
• Intermolecular Forces in Review 228

7 SOLIDS, LIQUIDS, AND PHASE

CHANGES 238
7.1 General Properties of the Condensed
Phases 239
7.2 Types of Solids 240
• Ionic Solids 240 • Molecular Solids 240
• Atomic Solids 242 • Network Solids 243
■ A Network Solid as Hard as Diamond 244
7.3 Physical Properties of Solids 247
• Vapor Pressure 247 • Melting Point 248
©Larry Keller, Lititz Pa./Getty Images
7.4 Physical Properties of Liquids 251
• Viscosity 251 • Surface Tension 251
■ Surface Tension and the Shape of Water Drops 252
• Vapor Pressure 253 • Boiling Point 254
■ High Altitude and High-Pressure Cooking 256
7.5 Energy and Physical Changes 257
• Temperature Changes 257 • Solid-Liquid Phase Changes: Melting
and Freezing 259 • Liquid-Gas Phase Changes: Vaporization and
Condensation 260 • Solid-Gas Phase Changes: Sublimation 261

8 GASES 272
8.1 Properties of Gases 273
• Gaseous Substances 274
• Kinetic Molecular Theory of Gases 275
8.2 Pressure 276
• Definition and Units of Pressure 276
• Measurement of Pressure 279
■ Fritz Haber 280
8.3 The Gas Equations 281
• The Ideal Gas Equation 281
■ Pressure Exerted by a Column of Fluid 285
©Eric Delmar/Getty Images
• The Combined Gas Equation 285
• The Molar Mass Gas Equation 286
8.4 The Gas Laws 289
• Boyle’s Law: The Pressure-Volume Relationship 289
• Charles’s Law: The Temperature-Volume Relationship 291
■ Automobile Air Bags and Charles’s Law 294
• Avogadro’s Law: The Moles-Volume Relationship 294
■ Amanda Jones 295
8.5 Gas Mixtures 297
• Dalton’s Law of Partial Pressures 297 • Mole Fractions 299
■ Hyperbaric Oxygen Therapy 300

xiv
9 PHYSICAL PROPERTIES OF SOLUTIONS 312
9.1 General Properties of Solutions 313
■ Honey – A Supersaturated Solution 314
■ Instant Hot Packs 315
9.2 Aqueous Solubility 315
9.3 Solution Concentration 316
• Percent by Mass 316
■ Trace Concentrations 317
• Molarity 319 • Molality 321 ©McGraw-Hill Education/Brian Rayburn, photographer
• Comparison of Concentration Units 321
9.4 Solution Composition 324
■ Robert Cade, M.D. 326
9.5 Solution Preparation 328
• Preparation of a Solution from a Solid 328 • Preparation of a
More Dilute Solution from a Concentrated Solution 329
Visualizing Chemistry – Preparing a Solution from a Solid 330
■ Serial Dilution 332
9.6 Colligative Properties 334
• Freezing-Point Depression 334 • Boiling-Point Elevation 335
■ Ice Melters 336
• Osmotic Pressure 337

10 CHEMICAL REACTIONS AND

CHEMICAL EQUATIONS 348
10.1 Recognizing Chemical Reactions 349
10.2 Representing Chemical Reactions with
Chemical Equations 352
• Metals 353 • Nonmetals 353
• Noble Gases 353 • Metalloids 353
10.3 Balancing Chemical Equations 354
■ The Stoichiometry of Metabolism 358
10.4 Types of Chemical Reactions 359
• Precipitation Reactions 359
• Acid-Base Reactions 364
■ Oxygen Generators 365
©Lindsay Upson/Getty Images
• Oxidation-Reduction Reactions 367
■ Antoine Lavoisier 372
■ Dental Pain and Redox 374
10.5 Chemical Reactions and Energy 376
10.6 Chemical Reactions in Review 376
11 USING BALANCED CHEMICAL EQUATIONS 386
11.1 Mole to Mole Conversions 387
11.2 Mass to Mass Conversions 389
11.3 Limitations on Reaction Yield 391
• Limiting Reactant 392 • Percent Yield 395
■ Combustion Analysis 397
■ Alka-Seltzer 398
11.4 Aqueous Reactions 400
11.5 Gases in Chemical Reactions 405
• Predicting the Volume of a Gaseous
Product 405 • Calculating the Required
Volume of a Gaseous Reactant 406
©Michael Donne/Science Source
■ Joseph Louis Gay-Lussac 408
11.6 Chemical Reactions and Heat 409

12 ACIDS AND BASES 420

12.1 Properties of Acids and Bases 421
■ James Lind 422
12.2 Definitions of Acids and Bases 423
• Arrhenius Acids and Bases 423
• Brønsted Acids and Bases 423
• Conjugate Acid-Base Pairs 424
12.3 Water as an Acid; Water as a Base 426
12.4 Strong Acids and Bases 428
12.5 pH and pOH Scales 431
©Aflo Co., Ltd./Alamy
■ Antacids and the pH Balance in Your
Stomach 438
■ Lake Natron 439
12.6 Weak Acids and Bases 440
12.7 Acid-Base Titrations 444
■ Using Millimoles to Simplify Titration Calculations 446
12.8 Buffers 447

xvi
13 EQUILIBRIUM 458
13.1 Reaction Rates 459

Visualizing Chemistry – Collision Theory 462

13.2 Chemical Equilibrium 464

■ How Do We Know That the Forward and
Reverse Processes Are Ongoing in a System
at Equilibrium? 466
13.3 Equilibrium Constants 466
■ Sweet Tea 467
©Eric Audras/Getty Images
• Calculating Equilibrium Constants 467
• Magnitude of the Equilibrium Constant 470
13.4 Factors That Affect Equilibrium 471
■ Hemoglobin Production at High Altitude 471
• Addition or Removal of a Substance 472
• Changes in Volume 474 • Changes in Temperature 475

14 ORGANIC CHEMISTRY 484

14.1 Why Carbon Is Different 485
14.2 Hydrocarbons 486
• Alkanes 487 • Alkenes and Alkynes 487
• Reactions of Hydrocarbons 489
14.3 Isomers 490
■ Partially Hydrogenated Vegetable Oils 491
■ Representing Organic Molecules with
Bond-Line Structures 493
14.4 Functional Groups 494
14.5 Alcohols and Ethers 495
©Andre Geim & Kostya Novoselov/Science Source
14.6 Aldehydes and Ketones 497
■ Percy Lavon Julian 498
14.7 Carboxylic Acids and Esters 499
14.8 Amines and Amides 500
14.9 Polymers 502
15 BIOCHEMISTRY 510
15.1 Biologically Important Molecules 511
• Glycerol 511 • Fatty Acids 511
• Amino Acids 511
■ Marie Maynard Daly 512
• Sugars 513 • Phosphates 513
• Organic Bases 513
15.2 Lipids 514
• Fats 514 • Phospholipids 515
• Steroids 516
15.3 Proteins 516
©hlansdown/Getty Images
• Primary Structure 519 • Secondary
Structure 519 • Tertiary Structure 519
• Quaternary Structure 520
15.4 Carbohydrates 520
• Monosaccharides 520 • Disaccharides 520 • Polysaccharides 521
15.5 Nucleic Acids 522

16 NUCLEAR CHEMISTRY 526

16.1 Radioactive Decay 527
16.2 Detection of Radiation and Its Biological
Effects 530
■ Radioactivity in Tobacco 532
16.3 Dating Using Radioactive Decay 532
16.4 Medical Applications of Radioactivity 534
■ How Nuclear Chemistry Is Used to
Treat Cancer 535
16.5 Nuclear Fission and Nuclear Fusion 535

Visualizing Chemistry – Nuclear Fission and

Fusion 536
■ Lise Meitner 538

©Andrey Gorulko/iStock/Getty Images

xviii
17 ELECTROCHEMISTRY 542
17.1 Balancing Oxidation-Reduction Reactions
Using the Half-Reaction Method 543
17.2 Batteries 547

Visualizing Chemistry – Construction of a

Galvanic Cell 548

• Dry Cells and Alkaline Batteries 551

• Lead Storage Batteries 552
• Lithium-Ion Batteries 553 • Fuel Cells 553
17.3 Corrosion 554
17.4 Electrolysis 556
• Electrolysis of Molten Sodium Chloride 556
©TEK IMAGE/Getty Images
• Electrolysis of Water 556

Appendix: Mathematical Operations A-1

Glossary G-1
Answers to Odd-Numbered Problems AP-1
Index I-1
Preface
Introductory Chemistry: An Atoms First Approach by Julia Burdge and Michelle Driessen
has been developed and written using an atoms first approach specific to introductory
chemistry. It is a carefully crafted text, designed and written with the introductory-
chemistry student in mind.

The arrangement of topics facilitates the conceptual development of chemistry for the
novice, rather than the historical development that has been used traditionally. Its lan-
guage and style are student friendly and conversational; and the importance and wonder
of chemistry in everyday life are emphasized at every opportunity. Continuing in the
Burdge tradition, this text employs an outstanding art program, a consistent problem-
solving approach, interesting applications woven throughout the chapters, and a wide
range of end-of-chapter problems.

Features
∙ Logical atoms first approach, building first an understanding of atomic structure,
followed by a logical progression of atomic properties, periodic trends, and how com-
pounds arise as a consequence of atomic properties. Following that, physical and chem-
ical properties of compounds and chemical reactions are covered—built upon a solid
foundation of how all such properties and processes are the consequence of the nature
and behavior of atoms.
∙ Engaging real-life examples and applications. Each chapter contains relevant, inter-
esting stories in Familiar Chemistry segments that illustrate the importance of chemis-
try to other fields of study, and how the current material applies to everyday life. Many
chapters also contain brief historical profiles of a diverse group of important people in
chemistry and other fields of scientific endeavor.
∙ Consistent problem-solving skill development. Fostering a consistent approach to
problem solving helps students learn how to approach, analyze, and solve problems.
282 CHAPTER 8 Gases
Each worked example (Sample Problem) is divided
into logical steps: Strategy, Setup, Solution, and
SAMPLE PROBLEM 8.2 Using the Ideal Gas Equation to Calculate Volume
Think About It; and each is followed by three prac-
Calculate the volume of a mole of ideal gas at room temperature (25°C) and 1.00 atm.
Strategy Convert the temperature in °C to temperature in kelvins, and use the ideal gas equation to solve for the unknown volume.
tice problems. Practice Problem A allows the stu-
Setup The data given are n = 1.00 mol, T = 298 K, and P = 1.00 atm. Because the pressure is expressed in atmospheres, we dent to solve a problem similar to the Sample
use R = 0.0821 L · atm/K · mol to solve for volume in liters.
Solution Problem, using the same strategy and steps. Wher-
Student Note: It is a very common mistake to fail to convert to

(1 mol) (0.0821
K · mol )
ever possible, Practice Problem B probes under-
absolute temperature when solving a gas problem. Most often,
L · atm temperatures are given in degrees Celsius. The ideal gas
(298 K)
equation only works when the temperature used is in kelvins.
V= = 24.5 L
1 atm Remember: K = °C + 273.
standing of the same concept(s) as the Sample
THI N K AB O UT I T Problem and Practice Problem A, but is sufficiently
With the pressure held constant, we should expect the volume to increase with increased temperature. Room temperature
is higher than the standard temperature for gases (0°C), so the molar volume at room temperature (25°C) should be higher
different that it requires a slightly different ap-
than the molar volume at 0°C—and it is.
proach. Practice Problem C often uses concept art
Practice Problem A TTEMPT What is the volume of 5.12 mol of an ideal gas at 32°C and 1.00 atm?
or molecular models, and probes comprehension of
Practice Problem B UILD At what temperature (in °C) would 1 mole of ideal gas occupy 50.0 L (P = 1.00 atm)? underlying concepts. The consistent use of this ap-
Practice Problem C ONCEPTUALIZE The diagram on the left represents a sample of gas in a container with a movable
piston. Which of the other diagrams [(i)–(iv)] best represents the sample (a) after the absolute temperature has been doubled; proach gives students the best chance for develop-
(b) after the volume has been decreased by half; and (c) after the external pressure has been doubled? (In each case, assume
that the only variable that has changed is the one specified.) ing a robust set of problem-solving skills.
∙ Outstanding pedagogy for student learning. The
Checkpoints and Student Notes throughout each
chapter are designed to foster frequent self-­
assessment and to provide timely information re-
garding common pitfalls, reminders of important
(i) (ii) (iii) (iv) information, and alternative approaches. Rewind and
Fast Forward links help to illustrate and reinforce
xx
SAMPLE PROBLEM 8.3 Using the Ideal Gas Equation to Calculate Pressure

Calculate the pressure of 1.44 mol of an ideal gas in a 5.00­L container at 36°C.
Strategy Rearrange the ideal gas law (Equation 8.1) to isolate pressure, P. Convert the temperature into kelvins, 36 + 273 = 309 K.
 Preface xxi

connections between material in different chapters, and enable students to find perti-
nent review material easily, when necessary.
∙ Key Skills pages are reviews of specific skills that the authors know will be important
to students’ understanding of later chapters. These go beyond simple reviews and actu-
ally preview the importance of the skills in later chapters. They are additional opportu-
nities for self-assessment and are meant to be revisited when the specific skills are
required later in the book.

Molecular Shape and Polarity KEY SKILLS Having determined molecular shape, we determine overall molecular polarity of each molecule by examining the individual
bond dipoles and their arrangement:
Cl
S H C C H C
Molecular polarity is tremendously important in determining the physical and chemical properties of a substance. Indeed, O O H Cl
molecular polarity is one of the most important consequences of molecular shape. To determine the shape of a molecule, H
we use a stepwise procedure:
1. Draw a correct Lewis structure [ Sections 6.1 and 6.2]. S and O have C and H have The C H bonds
2. Count electron groups on the central atom. Remember that an electron group can be a lone pair or a bond, and that electronegativity electronegativity are nonpolar. C
Determine whether values of 2.5 and values of 2.5 and and Cl have
a bond may be a single bond, a double bond, or a triple bond.
or not the 3.5, respectively. 2.1, respectively. electronegativity
3. Apply the VSEPR model [ Section 6.4] to determine electron-group geometry. Therefore, the Therefore, the values of 2.5 and
individual bonds
4. Consider the positions of the atoms to determine the molecular shape, which may or may not be the same as the are polar. bonds are polar. bonds are considered 3.0, respectively.
electron-group geometry. nonpolar. Therefore, the C Cl
Consider the examples of SO2, C2H2, and CH2Cl2. We determine the molecular shape of each as follows: bonds are polar.

Cl
Draw the Lewis
O S O H C C H H C Cl Only in C2H2 do the dipole-moment vectors cancel each other. C2H2 is nonpolar, SO2 and CH2Cl2 are polar.
structure
H
Even with polar bonds, a molecule may be nonpolar if it consists of equivalent bonds that are distributed symmetrically.
Molecules with equivalent bonds that are not distributed symmetrically—or with bonds that are not equivalent, even if they
3 electron groups: 2 electron groups on 4 electron groups: are distributed symmetrically—are generally polar.
Count the electron each central atom:
groups on the ∙ 1 double bond ∙ 1 single bond ∙ 4 single bonds
central atom(s) ∙ 1 single bond ∙ 1 triple bond
∙ 1 lone pair
Key Skills Problems
6.1 6.3
Apply VSEPR to 3 electron groups 2 electron groups 4 electron groups Determine the molecular shape of selenium dibromide. Which of the following species is polar?
determine electron- arrange themselves arrange themselves arrange themselves a) linear a) OBr2
group geometry in a trigonal plane. linearly. in a tetrahedron. b) bent b) GeCl4
c) trigonal planar c) SiO2
Cl d) trigonal pyramidal d) BH3
S e) tetrahedral e) BeF2
H C C H C
O O H Cl
H 6.2 6.4
Determine the molecular shape of phosphorus triiodide. Which of the following species is nonpolar?
With 1 lone pair on With no lone pairs With no lone pairs a) linear a) NCl3
Consider positions the central atom, on the central atom, on the central atom, b) bent b) SeCl2
of atoms to the molecular the molecular the molecular c) trigonal planar c) SO2
determine shape is bent. shape is linear. shape is tetrahedral. d) trigonal pyramidal d) CF4
molecular shape. e) tetrahedral e) AsBr3

233 234

bur48912_ch06_196-237.indd 233 8/29/18 7:52 PM bur48912_ch06_196-237.indd 234 8/29/18 7:52 PM

∙ Author-created online homework. All of the online homework problems were devel-
oped entirely by co-author Michelle Driessen to ensure seamless integration with the
book’s content.

A Student-Focused Revision
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users, were used to guide the revision. LearnSmart Heat Maps provided a quick visual
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xxiv Preface

New to This Edition

∙ Chapter 1 New graphics were added to illustrate the use of atomic number and mass
number; and to elucidate the concept of average atomic mass. The importance of dif-
ferent isotopes is now illustrated with an environmental example.
∙ Chapter 2 New graphics illustrate the process of determining and writing electron
configurations, and new arrows and highlights in the text make it easier for students to
understand the process. Improvements to Figure 2.1 clarify the relationship between
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 Acknowledgments
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College
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Meramec
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Community College District)

The following individuals helped write and review learning goal-oriented question content for this text’s SmartBook:

Margaret Ruth Leslie

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Additionally, we wish to thank our incredible team: Managing Director Kathleen McMahon, Executive Marketing
Manager Tami Hodge, Product Developer Marisa Dobbeleare, Program Manager Jolynn Kilburg, Senior Content Project
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Julia Burdge and Michelle Driessen

 CHAPTER
1
Atoms and Elements

1.1 The Study of Chemistry

• Why Learn Chemistry?
• The Scientific Method
1.2 Atoms First
1.3 Subatomic Particles and the Nuclear
Model of the Atom
1.4 Elements and the Periodic Table
1.5 Organization of the Periodic Table
1.6 Isotopes
1.7 Atomic Mass

The brilliant colors of a fireworks display result from the properties of the atoms
they contain. These atoms give off specific colors when they are burned.
©rozbyshaka/Getty Images
In This Chapter, You Will Learn
Some of what chemistry is and how it is studied using the scientific
method. You will learn about atomic structure and you will become
acquainted with the periodic table, how it is organized, and some
of the information it embodies.

Things To Review Before You Begin

• Basic algebra

Have you ever wondered how an automobile airbag works? Or why iron rusts when
exposed to water and air, but gold does not? Or why cookies “rise” as they bake? Or
what causes the brilliant colors of fireworks displays? These phenomena, and countless
others, can be explained by an understanding of the fundamental principles of chemistry.
Whether or not we realize it, chemistry is important in every aspect of our lives. In the
course of this book, you will come to understand the chemical principles responsible
for many familiar observations and experiences.

1.1 The Study of Chemistry

Chemistry is the study of matter and the changes that matter undergoes. Matter, in
turn, is anything that has mass and occupies space. Mass is one of the ways that sci-
entists measure the amount of matter.
You may already be familiar with some of the terms used in chemistry—even if
you have never taken a chemistry class. You have probably heard of molecules; and
even if you don’t know exactly what a chemical formula is, you undoubtedly know that
“H2O” is water. You may have used or at least heard the term chemical reaction; and
you are certainly familiar with many processes that are chemical reactions.

Why Learn Chemistry?

Chances are good that you are using this book for a chemistry class you are required
to take—even though you may not be a chemistry major. Chemistry is a required part
of many degree programs because of its importance in a wide variety of scientific
disciplines. It sometimes is called the “central science” because knowledge of chemis-
try supports the understanding of other scientific fields—including physics, biology,
geology, ecology, oceanography, climatology, and medicine. Whether this is the first in
a series of chemistry classes you will take or the only chemistry class you will ever
take, we hope that it will help you to appreciate the beauty of chemistry—and to
understand its importance in our daily lives.

The Scientific Method

Scientific experiments are the key to advancing our understanding of chemistry or any
science. Although different scientists may take different approaches to experimentation,
we all follow a set of guidelines known as the scientific method. This helps ensure the
quality and integrity of new findings that are added to the body of knowledge within
a given field.

4 CHAPTER 1 Atoms and Elements

The scientific method starts with the collection of data from careful observations
and/or experiments. Scientists study the data and try to identify patterns. When a pat-
tern is found, an attempt is made to describe it with a scientific law. In this context,
a law is simply a concise statement of the observed pattern. Scientists may then for-
mulate a hypothesis, an attempt to explain their observations. Experiments are then
designed to test the hypothesis. If the experiments reveal that the hypothesis is incor-
rect, the scientists must go back to the drawing board and come up with a different
interpretation of their data, and formulate a new hypothesis. The new hypothesis will
then be tested by experiment. When a hypothesis stands the test of extensive experi-
mentation, it may evolve into a scientific theory or model. A theory or model is a
unifying principle that explains a body of experimental observations and the law or
laws that are based on them. Theories are used both to explain past observations and
to predict future observations. When a theory fails to predict correctly, it must be
discarded or modified to become consistent with experimental observations. Thus, by
their very nature, scientific theories must be subject to change in the face of new data
that do not support them.
One of the most compelling examples of the scientific method is the development
of the vaccine for smallpox, a viral disease responsible for an estimated half a billion
deaths during the twentieth century alone. Late in the eighteenth century, English physi-
cian Edward Jenner observed that even during smallpox outbreaks in Europe, a particu-
lar group of people, milkmaids, seemed not to contract it.
Law: Milkmaids are not vulnerable to the virus that causes smallpox.
Based on his observations, Jenner proposed that perhaps milkmaids, who often
contracted cowpox, a similar but far less deadly virus, from the cows they worked with,
had developed a natural immunity to smallpox.
Hypothesis: Exposure to the cowpox virus causes the development of immunity
to the smallpox virus.
Jenner tested his hypothesis by injecting a healthy child with the cowpox virus—
and later with the smallpox virus. If his hypothesis were correct, the child would not
contract smallpox—and in fact the child did not contract smallpox.
Theory: Because the child did not develop smallpox, immunity seemed to have
resulted from exposure to cowpox.
Further experiments on many more people (mostly children and prisoners) con-
firmed that exposure to the cowpox virus imparted immunity to the smallpox virus.
The flowchart in Figure 1.1 illustrates the scientific method and how it guided
the development of the smallpox vaccine.

Hypothesis revised if Model altered if

experimental results experimental results
do not support it do not support it

Model (Theory)
Observations
Set of conceptual
Natural phenomena Experiment Further
Hypothesis assumptions that
and measured events; Procedure to test Experiment
Tentative explanation explains data from
if universally consistent, hypothesis; measures Tests predictions
that explains observations accumulated experiments;
can be stated one variable at a time based on model
predicts related
as a law
phenomena
Observation: Hypothesis: Experiment: Model: Further
Milkmaids don't Having contracted Intentionally expose Because child did not Experiment:
contract smallpox. cowpox, milkmaids a healthy child to cowpox contract smallpox, Many more humans
have a natural immunity and later to smallpox. immunity seemed to inoculated with
to smallpox. have resulted from cowpox virus, confirming
cowpox exposure. the model.

Figure 1.1
Another random document with
no related content on Scribd:
The same Spongicola lives in pairs in Hyalonema sieboldi. Another
case of apparently constant association is that of the Hydroid stocks
which inhabit Walteria. F. E. Schulze describes Stephanoscyphus
mirabilis (see p. 318) in a specimen of Walteria flemmingi; the
presence of the polyp causes the sponge to grow out into little dome-
shaped elevations, each of which shelters one polyp; while in W.
leuckarti Ijima finds a similar association in every specimen
examined.

Fossil Hexactinellida.
This group has the distinction of including among its Lyssacine
members the oldest known sponge, Protospongia fenestrata, of
Cambrian age (Salter). As preserved it consists of a single layer of
quadriradiate, or possibly quinqueradiate spicules, which, arranged
as a square meshed lattice, supported the superficial layer of the
sponge (Fig. 101). Whether or not the fossil represents the whole of
the sponge-skeleton does not appear.[236]

Fig. 101.—Part of the specimen of Protospongia fenestrata in the Sedgwick

Museum, Cambridge. Nat. size. (After Sollas.)

Fig. 102.—A portion of the outer surface of a Receptaculitid, Acanthoconia

barrandei, in which the expanded outer rays of the spicules are partially
destroyed, revealing the four tangential rays beneath, × 3. (After Hinde.)
The extraordinary Receptaculitidae are probably early Lyssacine
forms: they are cup- or saucer-shaped fossils, abundant in Silurian
and above all in Devonian strata, and have been "assigned in turn to
pine cones, Foraminifera, Sponges, Corals, Cystideans," and
Tunicata. Hinde[237] brings forward important arguments for retaining
them among Hexactinellida. The only elements in the skeleton of the
simpler genera, e.g. Ischadites, are structures comparable to
Hexactinellid spicules. The surface of the fossil presents a series of
lozenges forming a regular mosaic. Each lozenge is the expanded
end of one of the rays of a spicule; it conceals four rays in one plane,
tangential to the wall of the cup-shaped fossil, while the sixth ray
projects vertically to the wall into the cavity of the cup. In the genus
Receptaculites itself there is an inner layer of plates abutting against
the inner ends of the sixth rays, and at present problematic. An axial
canal is present in each of the rays—the six canals meeting at the
centre of the spicule. Special chinks between the spicules appear to
have provided a passage for the water current.

The beautiful Ventriculites, so common in the Chalk and present in

the Cambridge Greensand, are historically interesting, for the fact
that they are fossil Hexactinellida of which the general and skeletal
characters were very minutely described by Toulmin Smith long
before recent representatives of the group were known. In common
with a number of fossil Dictyonine species they are distinguished by
the perforation of the nodes, a character due to the fact that the
siliceous investment which unites the spicules together stops short
before reaching the centre of each spicule, and bridges across the
rays so as to form a skeleton octahedron. This character is rare in
recent Hexactinellids, but, as first pointed out by Carter, it is
presented by one or two forms, of which Aulocystis grayi Bwk is best
known. The majority of the fossil Hexactinellida belong to the
Dictyonine section, a fact attributable to the greater coherence of
their skeleton. The "Dictyonina" are to be reckoned among the rock-
builders of Jurassic and Cretaceous times.
 Fig. 103.—A node of the skeleton of Ventriculites from the Cambridge
Greensand. (After Sollas.)

The Octactinellida and Heteractinellida are two classes created by

Hinde[238] to contain certain little-known Devonian and
Carboniferous sponges, possessing in the one case 8-rayed
spicules, of which 6 rays lie in one plane and 2 are perpendicular to
this plane; in the other case, spicules with a number of rays varying
from 6 to 30. Bearing in mind the manner in which octactine spicules
are known to arise in recent Hexactinellida (p. 200), it is clearly
possible to derive these 8-rayed spicules from hexactines by some
similar method; while the typical spicule of the Heteractinellida is a
euaster. Hence we may refer the Octactinellid fossils to the class
Hexactinellida, and the Heteractinellid forms either to the
Monaxonida or Tetractinellida.

CLASS III. DEMOSPONGIAE

Silicispongiae in which triaxonid spicules are absent.

This class has attained the highest level of organisation known

among Porifera; the most efficient current-producing apparatus is
met with here, so, too, are protective coverings, stout coherent
skeletons, and the highest degree of histological differentiation found
in the phylum.

Correspondingly it is the most successful group, the majority of

existing sponges coming within its boundaries. A few genera and
species are exceedingly specialised, for example, Disyringa
dissimilis (p. 215). These, however, contribute only a very small
contingent to the Demosponge population, those species which are
really prolific and abundant being, as we should expect, the less
exaggerated types.

Canal System.—With a few exceptions the representatives of the

Demospongiae may be said to have taken up the evolution of the
canal system at the stage where it was left in Leucandra aspera—a
stage which the ancestral Demosponges must have reached quite
independently of the Calcarea. These commoner members are thus
already gifted with the advantages pertaining to a spherical form of
ciliated chamber, and so, too, is the Rhagon (Fig. 105), an immature
stage noteworthy as the simplest form of Demosponge, and thus the
starting-point for the higher types of canal system. The exceptions
above alluded to are not without interest: they are the
Dendroceratina, of doubtful affinities, (p. 220), which possess small
tubular Syconate chambers. They may be regarded either as of
independent origin from other Demospongiae, thus making the group
polyphyletic, or more simply as representing the ancestral condition,
and in this case we must look on the possession of spherical
chambers by the Rhagon as a secondary feature. Occupying as it
does the important position above indicated, the Rhagon merits a
brief description. It is a small discoid or hemispherical body attached
by a flat base. It contains a central paragaster, with a single osculum
at the free end. Into the paragaster open directly a few spherical
flagellated chambers, which lie in the lateral walls of the body. The
basal wall of the paragaster, the parts of its lateral walls between the
openings of neighbouring chambers, and the entire outer surface of
the body are covered with pinacocytes. It is convenient to call the
basal part of the sponge from which chambers are absent the
hypophare, the upper chamber-bearing part the spongophare. In
some of the deeper dermal cells spicules may be already present. In
the Rhagon, then, the canal system is of the second type, but all the
adult Demosponges have advanced to the third type, and the further
evolution in this system is in the direction of improving the mode of
communication of the chambers with the canal system. The changes
involved go hand in hand with increasing bulk of the dermal layer. A
glance at the accompanying figures will show at once the connexion
between the phenomena. The increase in the dermal layer (1)
greatly reduces the extent of the lumen of the excurrent canals; and
(2) results in the intervention of a narrow tube or aphodus between
the mouth of each chamber and the excurrent canal. The chamber
system is then converted from an "eurypylous" to an "aphodal" type.
When the incurrent canal also opens into the chamber by way of
narrow tubes, one proper to each chamber and termed "prosodus,"
the canal system is of the "diplodal" type.

Fig. 104.—Diagram of (A) eurypylous and (B) aphodal canal systems. a,

Apopyle; a', aphodus; E, excurrent canal; I, incurrent canal; p, prosopyle; p',
short prosodus. (After Sollas.)

Cortex.—All the stages in the formation of a cortex are to be seen

among the adult members of the group. Certain species (e.g. Plakina
monolopha, F.E.S.) are destitute even of an ectosome, others have a
simple dermal membrane (Halichondria panicea, Tetilla pedifera)
and various others are provided with a cortex, either of simple
structure or showing elaboration in one or more particulars. Thus a
protective armature of special spicules may be present in the cortex,
e.g. in Geodia, or to a less extent in Tethya, or there may be an
abundance of contractile elements, and these may be arranged in
very definite ways, forming valve-like apparatus that will respond to
stimuli.

Everywhere among sponges the goal of the skeleton appears to

have been coherence. We have seen how in Calcarea and in
Hexactinellida this has been attained by the secretion around the
separate elements of a continuous mineral sheath, calcareous in the
one case and siliceous in the other. Here we had an excellent
instance of the attainment of one end by similar means in two
different groups, after their separation from the common stock, and
therefore independently. In Demospongiae, on the other hand, the
same end—coherence—has been secured by two new methods,
each distinct from the former: first the spicules may be united in
strands by an organic deposit, spongin; secondly, the spicules may
assume irregular shapes and interlock closely with one another,
forming dense and stout skeletons. The latter method is that
characteristic of the Lithistid Tetractinellida.

Classification.—It is not of great moment which scheme of

classification we maintain, seeing that all hitherto proposed are
confessedly more or less artificial, and sufficient data for framing a
natural one are not yet forthcoming. For convenience, we accept
three subdivisions and define them thus:—

I. Tetractinellida.—Demospongiae possessing tetraxon or triaene spicules

or Lithistid desmas.
II. Monaxonida.—Demospongiae possessing monaxon but not tetraxon
spicules.
III. Ceratosa.—Demospongiae in which the main skeleton is formed of fibres
of spongin. The fibres may have a core of sand-grains or of foreign spicules,
but not of spicules proper to the sponge.

But at the same time we admit that some of the Ceratosa are
probably descended from some of the families of Monaxonida, so
that we should perhaps be justified in separating these families of
Monaxonida from the rest, and associating them with the allied
families of Ceratosa—a method of classification due to Vosmaer.
Again, some Monaxonida approximate to Tetractinellida, and we
might, with Vosmaer, unite them under the title Spiculispongiae. This
proceeding, though it has the advantage of being at least an attempt
to secure a natural classification, involves too much assumption
when carried out in detail to be wholly satisfactory.
 Sub-Class I. Tetractinellida.[239]
Tetractinellida appear to flourish best in moderate depths from 50 to
200 fathoms, but they are found to be fairly abundant also in
shallower water right up to the coast line, and in deep water up to
and beyond the 1000 fathom line. Occasionally they lie free on the
bottom, but are far more commonly attached; fixation may be direct
or by means of rooting spicules; the occurrence of a stalk is rare.
There is great variety in the root tuft, which may be a long loose wisp
of grapnel-headed spicules, as in many species of Tetilla, or a
massive tangle, as in Cinachyra barbata; in these cases the sponge
is merely anchored, so that it rests at the level of the surface of the
ooze; in other cases, e.g. Thenea wyvillei, the root tuft consists of a
number of pillars of spicules which raise the sponge above the level
of the ooze, into which they descend and there become continuous
with a large dense and confused mass of spicules. The parachute-
like base of Tetilla casula invites comparison with the "Crinorhiza"
forms of some Monaxonids (p. 216).

Two Orders are distinguished thus:—

I. Choristida.—Tetractinellida with quadriradiate spicules, which are never

articulated together into a rigid network.
II. Lithistida.—Tetractinellida with branching scleres (desmas), which may or
may not be modified tetrad spicules, articulated together to form a rigid
network. Triaene spicules may or may not be present in addition.

Order I. Choristida.
Plakina monolopha, from the Adriatic and Mediterranean, furnishes a
connecting link between the Rhagon stage and other Tetractinellida.
The choanosome is simply folded; there is no distinct ectosome; the
chambers are eurypylous. The skeleton consists of microcalthrops
and their derivatives. The hypophare is well developed. Plakina thus
shows a certain amount of resemblance to Oscarella (p. 196), with
which it shares the very remarkable possession of flagellated
pinacocytes.

One of the species of Tetilla, T. pedifera, continues the series. The

folds of its choanosome are more complicated than in P. monolopha,
and their outer ends are bridged together by a thin layer of ectosome
(cf. species of Sycon among Calcarea); the chambers are still
eurypylous.

The skeleton reaches a high level: it includes oxeas and triaenes

radiately disposed and microscleres (sigmata) scattered throughout
the dermal layer. The British Poecillastra compressa from the north
of Scotland and Orkney and Shetland is at about the same stage of
development, being without cortex and having eurypylous chambers,
but it is not so good an example, as the folds of its choanosome are
confused.

Fig. 105.—Diagrammatic vertical sections of A, Rhagon; B, Plakina; C, Tetilla

pedifera.

From T. pedifera we pass to the other species of Tetilla and all the
higher genera of Choristida; these possess a cortex not of
homologous origin in the various cases, but probably to be classified
under one of two heads, typified by Stelletta and Craniella
respectively (Fig. 106).
 Fig. 106.—A, Craniella type; B, Stellettid type. ch, Chone; co, collenchyma; d.o,
dermal ostia; fb, fibrous tissue; i.c, intercortical cavity; sd, subdermal cavity;
sp, sphincter. (After Sollas.)

In the Stellettids the cortex arises by the centrifugal growth of a

dermal membrane such as that of Tetilla pedifera; in Craniella
directly from the dermal tissue of the distal ends of the choanosomal
folds.

In both cases the end result, after completion of cell differentiation, is

a cortex either fibrous throughout or collenchymatous in its outer
portion and fibrous in the deeper layers. In the Stellettid type the
centrifugal growth of the dermal membrane involves the addition of
secondary distal portions to the ends of the inhalant passages.
These are the intercortical cavities or canals. Their most specialised
form is the "chone." A chone is a passage through the cortex
opening to the exterior by one or more ostia, and communicating
with the deeper parts of the inhalant system by a single aperture
provided with a sphincter (Fig. 106, B).

In the Craniella type the intercortical cavities are parts of the primary
inhalant system. They communicate with its deeper parts by
sphinctrate apertures. Without any knowledge of the development
one would certainly have supposed that the subdermal cavity, pore-
sieve and sphinctrate passages of Craniella represented a number
of chones, of which the outer portions had become fused (Fig. 106,
A).
 Fig. 107.—Disyringa dissimilis. Diagrammatic longitudinal section of the Sponge.
× ½. a, b, c, Transverse sections at the levels indicated to show subdivision
of the lumina of the excurrent and incurrent tubes; e.t, excurrent tube; i.t,
incurrent tube; o, osculum. (After Sollas.)

In both Craniella and Stelletta the chamber system is aphodal, and

these genera may fairly be taken as representatives of the average
level reached by Tetractinellida. The skeleton is of the radiate type:
the type which prevails in the Choristida, but which has an erratic
distribution, appearing in some genera of each family but not in
others. The genus Pachymatisma, of which we have the species P.
johnstonia and P. normani in these islands, exemplifies this; it
belongs to the highly differentiated family Geodiidae, possesses an
elaborate cortex with chones, but its main skeleton is non-radiate.

Disyringa dissimilis is remarkable for the perfection of its symmetry,

and for the absence of that multiplication of parts which is so
common among sponges. It possesses a single inhalant tube and a
single osculum (Fig. 107). Until quite recently it stood alone in the
restriction of its inhalant apertures to a single area. Kirkpatrick,
however, has now described a sponge—Spongocardium
gilchristi[240]—from Cape Colony, in which the dermal ostia are
concentrated in one sieve-like patch at the opposite pole to the
single osculum. Disyringa is still without companions in the
possession of an inhalant tube. The concentration of ostia into sieve
areas occurs again in Cinachyra, each sponge possessing in this
case several inhalant areas with or without scattered ostia also.

Order II. Lithistida.

The characteristic spicule of Lithistida—the desma—may be a
modified calthrop (tetracrepid desma), or it may be produced by the
growth of silica over a uniaxial spicule (rhabdocrepid desma) (Fig.
110, q), or it may be of the polyaxon type. It is probable that the
group is polyphyletic,[241] and that some of its members should
remain associated with Tetractinellida, while others should be
removed to Monaxonida. Forms with tetracrepid desmas, and those
forms with rhabdocrepid desmas which possess triaenes, have
Tetractinellid affinities, while forms possessing rhabdocrepid desmas
but lacking triaenes, and again those in which the desmas are
polyaxon, are probably descendants of Monaxonida.

Owing to the consistency of the skeleton Lithistida are frequently

found as fossils. The commonest known example is Siphonia.[242]
As in the case of so many other fossil sponges the skeleton is often
replaced by carbonate of lime, a fact which misled some of the
earlier investigators but was established by the researches of Sollas
and Zittel.

Sub-Class II. Monaxonida.[243]

The Monaxonida inhabit for the most part shallow water, but they
also extend through deep water into the abysses, thirteen species
having been dredged from depths of over 2000 fathoms by the
"Challenger" Expedition alone. In some cases, e.g. Cladorhiza,
Chondrocladia, all the species of a genus may live in deep water,
while in others the genus, or in others, again, the species, may have
a wide bathymetrical range. Thus Axinella spp. occur in shallow
water and in various depths down to 2385 fathoms, Axinella erecta
ranges from 90 to 1600 fathoms, Stylocordyla stipitata from 7 to
1600, and so on. The symmetry of the deep-water forms contrasts
strikingly with the more irregular shape of their shallow-water allies.
[244] The shallow-water species are almost always directly attached,
some few are stalked; those from deep water have either a long stalk
or some special device to save them from sinking in the soft ooze or
mud. Thus the deep-sea genus Trichostemma has the form of a low
inverted cone, round the base of which a long marginal fringe of
spicules projects, continuing the direction of the somal spicules, and
so forming a supporting rim. The same form has been independently
evolved in Halicnemia patera, and an approach to it in Xenospongia
patelliformis. A similar and more striking case of homoplasy is
afforded by the Crinorhiza form, which has been attained in certain
species of the deep-sea genera Chondrocladia, Axoniderma, and
Cladorhiza; here the sub-globular body is supported by a vertical
axis or root, and by a whorl of stout processes radiating outwards
and downwards from it, and formed of spicular bundles together with
some soft tissue.

There is recognisable in the order Monaxonida a cleft between one

set of genera, typically corticate, and suggesting by their structure a
relationship, whether of descent or parentage, with the
Tetractinellida, and a second set typically non-corticate: these latter
are the Halichondrina, the former are the Spintharophora.

Order I. Halichondrina.
We have already seen typical examples of the Halichondrina in
Halichondria panicea and Ephydatia fluviatilis. Within the
Halichondrina the development of spongin reaches its maximum
among spiculiferous sponges, and accordingly the Ceratosa take
their multiple origin here (p. 220). Among Halichondrina spongin co-
operates with spicules to form a skeleton in various ways, but always
so as to leave some spicules bare or free in the flesh. It may bind the
spicules end to end in delicate networks (as in Reniera or Gellius), or
into strands, sometimes reaching a considerable thickness (as in
Chalina and others). In a few cases there appears to be a kind of
division of labour between the spicules and spongin, the latter
forming the bulk of the fibre, i.e. fulfilling the functions of support,
while the spicules merely beset its surface as defensive organs,
rendering the sponge unfit for food. Fibres formed on this pattern are
called plumose, and are typical of Axinellidae. The distinctive fibre of
the Ectyoninae is as it were a combination of the Axinellid and
Chalinine types: a horny fibre both cored with spicules and beset
with them. Spicules besetting the surface of a fibre are termed
"echinating." Whenever its origin has been investigated, spongin has
proved to be the product of secretion of cells; in the great majority of
cases it is poured out at the surface of the cell, and Evans showed,
[245] at any rate in one species of Spongilla, that the spongin fibres
are continuous with a delicate cuticle at the surface of the sponge. In
Reniera spp. occurs a curious case of formation of spongin as an
intracellular secretion. A number of spherical cells each secrete
within themselves a short length of fibre; they then place themselves
in rows, so orientated that their contained rods lie end to end in one
line. The rods then fuse and make up continuous threads; the cells
diminish in breadth, ultimately leaving the fibre free.[246]

Order II. Spintharophora.

These corticate forms are further characterised by the arrangement
of their megascleres, which is usually, like that of most
Tetractinellida, radial, or approximating to radial. The microscleres
are, when present, some form of aster. The cortex resembles that of
Tetractinellida, and v. Lendenfeld has described chones in Tethya
lyncurium.[247]

The existence of the above points of resemblance between

Spintharophora and Tetractinellida suggests a relationship between
the two groups as its cause. In judging this possibility the following
reflections occur to us. A cortex exists in various independent
branches of Tetractinellida. It has in all probability had a different
phylogenetic history in each—why not then in these Monaxonida
also? Within single genera of Tetractinellida some species are
corticate, others not, witness Tetilla. The value of a cortex for
purposes of classification may easily be overestimated. If we are to
uphold the relationship between these two groups, we must base our
argument on the conjunction of similar characters in each.

The genus Proteleia[248] is interesting for its slender grapnel-like

spicules, which project beyond the radially disposed cortical
spicules, and simulate true anatriaenes of minute proportions. That
they are not anatriaenes is shown by the absence of an axial thread
in their cladi. It is not surprising that a form of spicule of such obvious
utility as the anatriaene should arise more than once.

Of exceptional interest, on account of their boring habit, are the

Clionidae. How the process of boring is effected is not known; the
presence of an acid in the tissues was suspected, but has been
searched for in vain. The pieces of hard substance removed by the
activity of the sponge take their exit through the osculum and have a
fixed shape[249] (Fig. 108).

As borers into oyster shells, Clionidae may be reckoned as pests of

practical importance, and in some coasts they even devastate the
rocks, penetrating to a depth of some feet, and causing them to
crumble away.[250]

Sponges, however, as agents in altering the face of the earth do not

figure as destroyers merely. On the contrary, it has been
calculated[251] that sponge skeletons may give rise with
considerable rapidity to beds of flint nodules; in fact, it appears that a
period so short as fifty years is sufficient for the formation of a bed of
flints out of the skeletons of sponges alone.

Suberites domuncula is well known for its constant symbiosis with

the Hermit crab. The young sponge settles on a Whelk or other shell
inhabited by a Pagurus, and gradually envelops it, becoming very
massive, and completely concealing the shell, without however
closing its mouth. The aperture of this always remains open to the
exterior, however great the growth of the sponge, a tubular passage
being left in front of it, which continues the lumen of the shell and
maintains its spiral direction. When the crab has grown too big for
the shell, it merely advances a little down this passage. The shell is
never absorbed, as was once supposed.[252] The crab, besides
being provided with a continually growing house, and being thus
spared the great dangers attending a shift of lodgings, benefits
continually by the concealment and protection afforded by the
massive sponge; the latter in return is conveyed to new places by
the crab.

Fig. 108.—A, calcareous corpuscle detached by Cliona; B, view of the galleries

excavated by the Sponge. (After Topsent.)

Ficulina ficus is sometimes, like S. domuncula, found in symbiosis

with Pagurus, but the constancy of the association is wanting in this
case. The sponge has several metamps, one of which, from its fig-
like shape, gives it its name.

Sub-Class III. Ceratosa.

The Ceratosa are an assemblage of ultimate twigs shorn from the
branches of the Monaxonid tree. They are therefore related forms,
but many of them are more closely connected with their Monaxonid
relatives than with their associates in their own sub-class.

The genera Aulena and Phoriospongia, placed by v. Lendenfeld

among Ceratosa, by Minchin among Monaxonida, show each in its
own way how close is the link between these two sub-classes.
Aulena possesses in its deeper parts a skeleton of areniferous
spongin fibres, in fact a typical Ceratose skeleton; but this is
continuous with a skeleton in the more superficial parts, which is
composed of spongin fibres echinated by spicules proper to the
sponge, and precisely comparable to the ectyonine fibres of some
Monaxonida.

Phoriospongia, as far as its main skeleton is concerned, is a typical

Ceratose sponge, with fibres of the areniferous type, but it
possesses sigmata free in the flesh.

The sub-class is confined to shallow water, no horny sponge having

been dredged from depths greater than 410 fathoms.[253] The
greatest number occur at depths between 10 and 26 fathoms.

In the majority of the Ceratosa the skeletal fibres are homogeneous,

formed of concentric lamellae of spongin, deposited by a sheath of
spongoblasts around a filiform axis. In others, however, the axis
attains a considerable diameter, so as to form a kind of pith to the
fibre, which is then distinguished as heterogeneous. In one or two
cases some of the spongoblasts of a heterogeneous fibre are
included in the fibre between the spongin lamellae. Ianthella is the
best-known example in which this occurs.

Ceratosa are divided into Dictyoceratina and Dendroceratina,

distinguished, as their names express, by the nature of the skeleton
—net-like, with many anastomoses, in the one; tree-like, without
anastomoses between its branches, in the other.

The Dictyoceratina comprise by far the larger number of Ceratosa.

They fall into two main families, the Spongidae and Spongelidae,
both represented in British waters. The Spongidae are characterised
by a granular ground substance and aphodal chamber system; the
Spongelidae by a clear ground substance and sac-like eurypylous
chambers.
The bath sponge, Euspongia officinalis, belongs to the Spongidae.
The finest varieties come from the Adriatic, the coarser ones from
the Dalmatian and North African coasts of the Mediterranean, from
the Grecian Archipelago, from the West Indies, and from Australian
seas. The softer species of the genus Hippospongia also form a
source of somewhat inferior bath sponges.

Among Dendroceratina, Darwinella is unique and tempts to

speculation, in that it possesses isolated spongin elements,
resembling in their forms triaxon spicules.

Key to British Genera of Sponges.

1. (a) Skeleton calcareous 2

(b) Skeleton siliceous 6
(c) Skeleton horny, or without free 53
spicules
(d) Skeleton absent 55
2. (a) Gastral layer continuous 3
(b) Gastral layer discontinuous, 4
confined to chambers
3. (a) Equiangular triradiate systems Clathrina
present
(b) Triradiate systems all alate Leucosolenia
4. (a) Chambers tubular, radially 5
arranged
(b) Chambers spherical, irregularly Leucandra
scattered
5. (a) Tufts of oxeate spicules at the Sycon
ends of the chambers
(b) Oxeate spicules lying Ute
longitudinally in the cortex
6. (a) All the spicules hexradiate or 7
 spicules easily derived from
hexradiate type
(b) Some of the spicules calthrops or 10
triaenes
(c) Megascleres uniaxial 15
7. (a) Amphidiscs present 8
(b) Amphidiscs absent 9
8. (a) Rooting spicules a well-defined Hyalonema thomsoni
wisp; four apertures lead into the
gastric cavity
(b) Rooting tuft diffuse; sponge oval; Pheronema carpenteri
osculum single
9. (a) Sponge tubular, dermal and Euplectella suberea
gastral pinuli absent
(b) Sponge a widely open cup; Asconema setubalense
dermal and gastral pinuli present
10.(a) Tetractine spicule, a calthrop or Dercitus bucklandi
triaene with short rhabdome;
microsclere a spined microxea
(b) Triaenes with fully developed 11
rhabdome

Fig. 109.—Microscleres of Demospongiae. a, b, Sigmaspires viewed in different

directions; c, d, bipocilli viewed in different directions; e, toxaspire; f, f',
spiraster; g, sanidaster; h, amphiaster; i, sigma; j, diaucistra; k, isochela; l,
m, anisochelae viewed in different directions; n, cladotyle; o, toxa; p,
 forceps; q, oxyaster; r, spheraster; s, oxyaster with 6 actines; t, another with
4 actines; u, another with rays reduced to two (centrotylote microxea); v,
tylote microrhabdus; w, trichodragmata; x, oxeate microrhabdus or
microxea.

11.(a) Microscleres sigmata Craniella cranium

(b) Sigmata absent, asters present 12
12.(a) Microscleres include spirasters Poecillastra compressa
(b) Microscleres include sterrasters 14
(c) Microscleres include euasters: 13
spirasters and sterrasters
absent
13.(a) Two kinds of euaster present Stelletta
(b) Microscleres include a euaster Stryphnus ponderosus
and a sanidaster or
amphiaster
14.(a) Microscleres include Pachymatisma johnstonia
microrhabdi
(b) Microscleres include many- Cydonium milleri
rayed euasters
15.(a) Some of the microscleres 16
asters
(b) Microscleres absent, or not 17
asters
16.(a) Skeleton radiate; asters of Tethya
more than one kind
(b) Sponge encrusting; asters of Hymedesmia
one kind only
(c) Skeleton fibrous Axinella spp.
17.(a) Megascleres all diactinal; Desmacidon
chelae present
(b) Megascleres all diactinal; 18
chelae absent
(c) Some or all of the megascleres 19
 monactinal
18.(a) Habitat fresh water 56
(b) Habitat marine 22
19.(a) Megascleres include cladotyles Acarnus
(b) Megascleres include dumb-bell Plocamia
or sausage-shaped spicules
forming the main reticulum
(c) Microscleres include bipocilli 20
(d) Microscleres include diancistra Hamacantha
(e) Megascleres include forceps Forcepia
(f) Skeleton formed of isolated Hymeraphia
monactines vertically placed
(g) None of the above peculiarities 21
present
20.(a) Skeleton fibre not echinated Iophon
(b) Skeleton fibre echinated Pocillon
21.(a) Skeleton with echinating 28
spicules
(b) Skeleton without echinating 30
spicules
22.(a) Spongin abundant 23
(b) Spongin scanty 25
23.(a) Fibre not echinated 24
(b) Fibre echinated Diplodemia
24.(a) Fibre with a single axial series Chalina
of spicules
(b) Fibres with numerous spicules Pachychalina
arranged polyserially
25.(a) Microscleres absent 26
(b) Microscleres sigmata and/or 27
toxa
26.(a) Skeleton confused Halichondria
(b) Skeleton reticulate Reniera